Method of processing adulterated biomass feedstocks

ABSTRACT

A method is provided that involves contacting a feed stream including a biorenewable feedstock and adulterants with a catalyst in a fixed bed hydroprocessing reactor to produce a hydroprocessed product with less adulterants than the feed stream.

FIELD

The present technology relates generally to the processing ofadulterated biorenewable feedstocks for manufacture of high qualityhydroprocessed products. More particularly, and not by way oflimitation, the present technology provides a method to produce a highquality hydroprocessed product with less adulterants than the feedstream.

BACKGROUND

Biomass is a renewable alternative to fossil raw materials in theproduction of fuels and chemicals. The increase of renewable productsand biofuels production is part of the government's strategy ofsustainability, improving energy security and reducing greenhouse gasemissions.

However, there is the potential for many sources of biomass to becomecontaminated with manufactured adulterants due to handling andprocessing. These adulterants can negatively impact both theprocessibility of the biomass feedstock and the performance of thefinished products. Therefore, a great deal of time and expense has beeninvested in pretreatment of biomass to remove potential adulterants aswell as native components that can negatively impact production (e.g.phosphorus, metals).

SUMMARY

In one aspect, a method is provided involving contacting a feed streamcomprising a biorenewable feedstock and adulterants with a catalyst in afixed bed hydroprocessing reactor to produce a hydroprocessed productwith less adulterants than the feed stream; wherein the fixed bedreactor is at a temperature less than about 750° F. (400° C.) and thefixed bed hydroprocessing reactor is at a pressure from about 200 psig(13.8 barg) to about 4,000 psig (275 barg).

In some embodiments, the hydroprocessed product comprises at least 80 wt% paraffins falling within the range of C₁₁ to C₂₄, where the paraffinscomprise C₁₆ and C₁₈ paraffins; from about 0.1 wt % to about 7.0 wt %cycloparaffins; and from about 0.001 wt % to about 1.0 wt % aromatics.In some embodiments of such a hydroprocessed product, the hydroprocessedproduct is suitable for use as a diesel fuel.

In some embodiments, the adulterants include polymers, monomers ofpolymers, drugs, pesticides, polymer additives, food preservatives, ormixtures of any two or more thereof. In some embodiments, theadulterants comprise acrylonitrile butadiene styrene thermoplastic,polyacrylate rubber, ethylene-acrylate rubber, polyester urethane, bromoisobutylene isoprene rubber, polybutadiene rubber, chloro isobutyleneisoprene rubber, polychloroprene, chlorosulphonated polyethylene,epichlorohydrin, ethylene propylene rubber, ethylene propylene dienemonomer, polyether urethane, tetrafluoroethylene/propylene rubbers,perfluorocarbon elastomers, fluoroelastomer, fluoro silicone,fluorocarbon rubber, high density polyethylene, hydrogenated nitrilebutadiene, polyisoprene, isobutylene isoprene rubber, low densitypolyethylene, polyethylene terephthalate, ethylene vinyl acetate,acrylonitrile butadiene, polyethylene, polyisobutene, polypropylene,polystyrene, poly vinyl choloride, polyvinylidene chloride,polyurethane, styrene butadiene, styrene ethylene butylene styrenecopolymer, polysiloxane, vinyl methyl silicone, acrylonitrile butadienecarboxy monomer, styrene butadiene carboxy monomer, thermoplasticpolyether-ester, styrene butadiene block copolymer, styrene butadienecarboxy block copolymer, polyesters, polyamides, polyacetals, ormixtures of any two or more thereof. In some embodiments, theadulterants include polyvinylidene chloride.

In some embodiments, the adulterants comprise a polymer additive. Insome embodiments, the adulterants comprise acetamide, benzyl benzoate,benzyl butyl phthalate, bis(2-ethylhexyl)adipate,bis(2-ethylhexyl)phthalate, bisphenol A, bisphenol AF, 1,2-cyclohexanedicarboxylic acid diisononyl ester, dibutyl phthalate, dibutyl sebacate,diethylene glycol dinitrate, diisobutyl phthalate, diisodecyl phthalate,diisononyl phthalate, dimethyl methylphosphonate, 2,4-dinitrotoluene,dioctyl adipate, diisodecyl adipate, dioctyl terephthalate, dipropyleneglycol, epoxidized soybean oil, ethyl butyrate, ethylene carbonate,furoin, neopentyl glycol, phthalate, polybutene, polycaprolactone,propylene carbonate, triacetin, tributyl phosphate, tricresyl phosphate,triethyl phosphate, triethylene glycol dinitrate, trimethylolethanetrinitrate, asbestine, barium borate, brominated flame retardant,bromoform, calcium borate, chlorendic acid, decabromodiphenyl ether,1,2-dibromoethane, dimethyl chlorendate, dimethyl methylphosphonate,heptazine, hexabromocyclododecane, octabromodiphenyl ether,pentabromodiphenyl ether, polybrominated biphenyl, polybrominateddiphenyl ethers, polychlorinated biphenyl, tetrabromobisphenol A,tris(2,3-dibromopropyl) phosphate, tris(2-chloroethyl) phosphate, zincborate, or mixtures of any two or more thereof.

In some embodiments, the adulterants include pesticides. In someembodiments, the adulterants include acephate, acetochlor, aldicarb,atrazine, bifenthrin, chloropicrin, chlorothalonil, chlorphyrifos,2,4-dichlorophenoxyacetic acid, dichloropropene, dimethenamid, diuron,ethephon, fenoxycarb, glyphosate, 2-methyl-4-chlorophenoxyacetic acid,metham sodium, metham potassium, methyl bromide, metolachlor, paraquat,pendimethalin, propanil, simazine, trifluralin, or mixtures of any twoor more thereof. In some embodiments, the adulterants include a polymerand a polymer additive.

In some embodiments, from about 100 to about 15,000 reactor volumes ofbiorenewable feedstock are processed prior to shutdown of the fixed bedhydroprocessing reactor. In some embodiments, the liquid hourly spacevelocity of the feed stream through the fixed bed hydroprocessingreactor is from about 0.2 hr⁻¹ to about 10.0 hr⁻¹. In some embodiments,the reactor comprises a hydrotreatment catalyst.

In some embodiments, the biorenewable feedstock comprises animal fats,animal oils, plant fats, plant oils, vegetable fats, vegetable oils, orgreases. In some embodiments, the biorenewable feedstock comprisesanimal fats, poultry oil, soybean oil, canola oil, rapeseed oils, palmoil, palm kernel oil, jatropha oil, castor oil, camelina oil, algae oil,seaweed oil, halophile oils, rendered fats, restaurant greases, browngrease, yellow grease, waste industrial frying oils, fish oils, talloil, or tall oil fatty acids. In some embodiments, the biorenewablefeedstock comprises animal fats, restaurant greases, brown grease,yellow grease, or waste industrial frying oils. In some embodiments, thebiorenewable feedstock comprises the fatty acid distillate fromvegetable oil deodorization.

In some embodiments, the hydroprocessed product is suitable as a dieselfuel, a diesel fuel additive, a diesel fuel blendstock, a turbine fuel,a turbine fuel additive, a turbine fuel blendstock, an aviation fuel, anaviation fuel additive, or an aviation fuel blendstock. In someembodiments, the hydroprocessed product is fractionated to provide amiddle distillate fraction. In some embodiments, the middle distillatefraction is suitable for use as a diesel fuel.

In some embodiments, the feed stream further comprises a diluent and thevolume ratio of diluent to biorenewable feedstock falls within the rangefrom about 0.5:1 to about 20:1.

BRIEF DESCRIPTION OF THE FIGURES

FIGS. 1A and 1B illustrate solids contaminants which may becomeassociated with fats and oils and greases (FOG).

FIG. 2 illustrates the concentrations of dissolved polyethylene fromsamples of animal fats, fish oils, yellow greases, vegetable oils, andwaste vegetable oils, according to the Examples.

DETAILED DESCRIPTION

Various embodiments are described hereinafter. It should be noted thatthe specific embodiments are not intended as an exhaustive descriptionor as a limitation to the broader aspects discussed herein. One aspectdescribed in conjunction with a particular embodiment is not necessarilylimited to that embodiment and can be practiced with any otherembodiment(s).

As used herein, “about” will mean up to plus or minus 10% of theparticular term.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the elements (especially in the context of thefollowing claims) are to be construed to cover both the singular and theplural, unless otherwise indicated herein or clearly contradicted bycontext. Recitation of ranges of values herein are merely intended toserve as a shorthand method of referring individually to each separatevalue falling within the range, unless otherwise indicated herein, andeach separate value is incorporated into the specification as if it wereindividually recited herein. All methods described herein can beperformed in any suitable order unless otherwise indicated herein orotherwise clearly contradicted by context. The use of any and allexamples, or exemplary language (e.g., “such as”) provided herein, isintended merely to better illuminate the embodiments and does not pose alimitation on the scope of the claims unless otherwise stated. Nolanguage in the specification should be construed as indicating anynon-claimed element as essential.

As used herein, “alkyl” groups include straight chain and branched alkylgroups having from 1 to about 22 carbon atoms. As employed herein,“alkyl groups” include cycloalkyl groups as defined below. Alkyl groupsmay be substituted or unsubstituted. Examples of straight chain alkylgroups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl,n-heptyl, and n-octyl groups. Examples of branched alkyl groups include,but are not limited to, isopropyl, sec-butyl, t-butyl, neopentyl, andisopentyl groups.

Cycloalkyl groups are cyclic alkyl groups such as, but not limited to,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, andcyclooctyl groups. In some embodiments, the cycloalkyl group has 3 to 8ring members, whereas in other embodiments the number of ring carbonatoms range from 3 to 5, 6, or 7. Cycloalkyl groups further includepolycyclic cycloalkyl groups such as, but not limited to, norbornyl,adamantyl, bornyl, camphenyl, isocamphenyl, and carenyl groups, andfused rings such as, but not limited to, decalinyl, and the like.Cycloalkyl groups also include rings that are substituted with straightor branched chain alkyl groups as defined above.

The term “aromatics” as used herein is synonymous with “aromates” andmeans both cyclic aromatic hydrocarbons that do not contain heteroatomsas well as heterocyclic aromatic compounds. The term includesmonocyclic, bicyclic and polycyclic ring systems. The term also includesaromatic species with alkyl groups and cycloalkyl groups. Thus,aromatics include, but are not limited to, benzene, azulene, heptalene,phenylbenzene, indacene, fluorene, phenanthrene, triphenylene, pyrene,naphthacene, chrysene, anthracene, indene, indane, pentalene, andnaphthalene, as well as alkyl and cycloalkyl substituted variants ofthese compounds. In some embodiments, aromatic species contains 6-14carbons, and in others from 6 to 12 or even 6-10 carbon atoms in thering portions of the groups. The phrase includes groups containing fusedrings, such as fused aromatic-aliphatic ring systems (e.g., indane,tetrahydronaphthene, and the like).

“Oxygenates” as used herein means carbon-containing compounds containingat least one covalent bond to oxygen. Examples of functional groupsencompasses by the term include, but are not limited to, carboxylicacids, carboxylates, acid anhydrides, aldehydes, esters, ethers,ketones, and alcohols, as well as heteroatom esters and anhydrides suchas phosphate esters and phosphate anhydrides. Oxygenates may also beoxygen containing variants of aromatics, cycloparaffins, and paraffinsas described herein.

The term “paraffins” as used herein means non-cyclic, branched orunbranched alkanes. An unbranched paraffin is an n-paraffin; a branchedparaffin is an iso-paraffin. “Cycloparaffins” are cyclic, branched orunbranched alkanes.

The term “paraffinic” as used herein means both paraffins as definedabove as well as predominantly hydrocarbon chains possessing regionsthat are alkane, either branched or unbranched, with mono- ordi-unsaturation (i.e. one or two double bonds), halogenation from about30 wt % to about 70 wt %, or where the hydrocarbon is both unsaturatedand halogenated. However, the term does not describe a halogen on acarbon involved in a double bond. The term also encompasses alkylalcohols, alkyl carboxylic acids, alkyl aldehydes, alkyl ketones, alkylesters, and alkyl ethers.

Adulterants as used herein refer to human synthesized compounds andsubstances that may become associated with a biorenewable feedstock.Examples of adulterants include, but are not limited to, polymers,oligomers, additives associated with polymers and oligomers, (e.g.plasticizers; inorganic additives incorporated into a polymer), residualmonomers or plasticizers incorporated into the polymers and oligomers,pesticides (also known as biocides, and including but not limited toinsecticides, fumigants, fungicides, herbicides, and plant growthregulators), preservatives, drugs, man-made halogenated organics, andman-made organometallic complexes.

Hydroprocessing as used herein describes the various types of catalyticreactions that occur in the presence of hydrogen without limitation.Examples of the most common hydroprocessing reactions include, but arenot limited to, hydrogenation, hydrodesulfurization (HDS),hydrodenitrogenation (HDN), hydrotreating (HT), hydrocracking (HC),aromatic saturation or hydrodearomatization (HDA), hydrodeoxygenation(HDO), decarboxylation (DCO), hydroisomerization (HI), hydrodewaxing(HD), hydrodemetallization (HDM), decarbonylation, methanation, andreforming. Depending upon the type of catalyst, reactor configuration,reactor conditions, and feedstock composition, multiple reactions cantake place that range from purely thermal (i.e. do not require catalyst)to catalytic. In the case of describing the main function of aparticular hydroprocessing unit, for example an HDO reaction system, itis understood that the HDO reaction is merely one of the predominantreactions that are taking place and that other reactions may also takeplace.

Decarboxylation (DCO) is understood to mean hydroprocessing of anorganic molecule such that a carboxyl group is removed from the organicmolecule to produce CO₂, as well as decarbonylation which results in theformation of CO.

Pyrolysis is understood to mean thermochemical decomposition ofcarbonaceous material with little to no diatomic oxygen or diatomichydrogen present during the thermochemical reaction. The optional use ofa catalyst in pyrolysis is typically referred to as catalytic cracking,which is encompassed by the term as pyrolysis, and is not be confusedwith hydrocracking

Hydrotreating (HT) involves the removal of elements from groups 3, 5, 6,and/or 7 of the Periodic Table from organic compounds. Hydrotreating mayalso include hydrodemetallization (HDM) reactions. Hydrotreating thusinvolves removal of heteroatoms such as oxygen, nitrogen, sulfur, andcombinations of any two more thereof through hydroprocessing. Forexample, hydrodeoxygenation (HDO) is understood to mean removal ofoxygen by a catalytic hydroprocessing reaction to produce water as aby-product; similarly, hydrodesulfurization (HDS) andhydrodenitrogenation (HDN) describe the respective removal of theindicated elements through hydroprocessing.

Hydrogenation involves the addition of hydrogen to an organic moleculewithout breaking the molecule into subunits. Addition of hydrogen to acarbon-carbon or carbon-oxygen double bond to produce single bonds aretwo nonlimiting examples of hydrogenation. Partial hydrogenation andselective hydrogenation are terms used to refer to hydrogenationreactions that result in partial saturation of an unsaturated feedstock.For example, vegetable oils with a high percentage of polyunsaturatedfatty acids (e.g. linoleic acid) may undergo partial hydrogenation toprovide a hydroprocessed product wherein the polyunsaturated fatty acidsare converted to mono-unsaturated fatty acids (e.g. oleic acid) withoutincreasing the percentage of undesired saturated fatty acids (e.g.stearic acid). While hydrogenation is distinct from hydrotreatment,hydroisomerization, and hydrocracking, hydrogenation may occur amidstthese other reactions.

Hydrocracking (HC) is understood to mean the breaking of a molecule'scarbon-carbon bond to form at least two molecules in the presence ofhydrogen. Such reactions typically undergo subsequent hydrogenation ofthe resulting double bond.

Hydroisomerization (HI) is defined as the skeletal rearrangement ofcarbon-carbon bonds in the presence of hydrogen to form an isomer.Hydrocracking is a competing reaction for most HI catalytic reactionsand it is understood that the HC reaction pathway, as a minor reaction,is included in the use of the term HI. Hydrodewaxing (HDW) is a specificform of hydrocracking and hydroisomerization designed to improve the lowtemperature characteristics of a hydrocarbon fluid.

Hydrocarbonaceous is defined as being primarily composed of organicmolecules containing carbon and hydrogen (i.e. hydrocarbon), but alsoinclude constituents of other organic molecules such as those comprisedof atoms selected from groups 3 through group 7 of the Periodic Table(e.g. boron, nitrogen, oxygen, phosphorus, sulfur, and/or halogens).

“Aviation fuel” as used herein includes both jet fuel and aviationgasoline. Jet fuel also goes by the term aviation turbine fuel.

“Turbine fuel” as used herein includes, but is not limited to, a fuelcombusted with compressed air to drive an electric generator, or topower ships and tanks. Turbine fuels are typically diesel or keroseneboiling range fuels.

The present technology provides methods and systems for thehydroprocessing of feed streams that include adulterants, such that thehydroprocessed product produced has less adulterants. Accordingly, thepresent technology also provides compositions with a reduced level ofadulterants. Contrary to the requirements for purified biorenewablefeedstocks, the present technology allows for the processing ofcontaminated, and therefore cheaper, biorenewable feedstocks.

Thus, in an aspect, a method is provided that involves contacting a feedstream, where the feed stream includes a biorenewable feedstock andadulterants, with a catalyst in a fixed bed hydroprocessing reactor toproduce a hydroprocessed product with less adulterants than the feedstream. The fixed bed hydroprocessing reactor is at a temperature lessthan about 750° F. (400° C.), and is at a pressure from about 200 psig(13.8 barg) to about 4,000 psig (275 barg). The hydroprocessed productpossesses less adulterants than the feed stream in its undistilled form,although in some embodiments the hydroprocessed product may be furtherdistilled. In some embodiments, the fixed bed hydroprocessing reactor isa continuous fixed bed hydroprocessing reactor. In some embodiments, thehydroprocessed product is suitable as a diesel fuel, a diesel fueladditive, a diesel fuel blendstock, a turbine fuel, a turbine fueladditive, a turbine fuel blendstock, an aviation fuel, an aviation fueladditive, an aviation fuel blendstock, or a combination of any two ormore thereof.

In some embodiments, the process converts at least a portion of theadulterants into hydroprocessed product. In some such embodiments, themethod converts at least about 0.01 wt % of the adulterants intohydroprocessed product. The weight percent of the adulterants convertedinto hydroprocessed product may be about 0.05 wt %, about 0.1 wt %,about 0.5 wt %, about 1 wt %, about 5 wt %, about 10 wt %, about 15 wt%, about 20 wt %, about 25 wt %, about 30 wt %, about 35 wt %, about 40wt %, about 45 wt %, about 50 wt %, about 55 wt %, about 60 wt %, about65 wt %, about 70 wt %, about 75 wt %, about 80 wt %, about 85 wt %,about 90 wt %, about 95 wt %, about 98 wt %, about 99 wt %, or anyranges including and in between any two of these values or above any oneof these values.

The amount of adulterants in the feed stream may be about 0.01 wppmbased on the biorenewable feedstock. The amount of adulterants as basedon the biorenewable feedstock may be about 0.05 wppm, about 0.1 wppm,about 0.5 wppm, about 0.1 wppm, about 5 wppm, about 10 wppm, about 15wppm, about 20 wppm, about 25 wppm, about 30 wppm, about 35 wppm, about40 wppm, about 45 wppm, about 50 wppm, about 55 wppm, about 60 wppm,about 65 wppm, about 70 wppm, about 75 wppm, about 80 wppm, about 85wppm, about 90 wppm, about 95 wppm, about 100 wppm, about 105 wppm,about 110 wppm, about 115 wppm, about 120 wppm, about 125 wppm, about130 wppm, about 135 wppm, about 140 wppm, about 145 wppm, about 150wppm, about 155 wppm, about 160 wppm, about 165 wppm, about 170 wppm,about 175 wppm, about 180 wppm, about 185 wppm, about 190 wppm, about195 wppm, about 200 wppm, about 225 wppm, about 250 wppm, about 275wppm, about 300 wppm, about 325 wppm, about 350 wppm, about 375 wppm,about 400 wppm, about 425 wppm, about 450 wppm, about 475 wppm, about500 wppm, about 550 wppm, about 600 wppm, about 650 wppm, about 700wppm, about 750 wppm, about 800 wppm, about 850 wppm, about 900 wppm,about 1000 wppm, and ranges including and between any two of thesevalues and above any one of these values.

The amount of adulterants in the feed stream may be reduced by about0.01%. The amount of adulterants may be reduced by about 0.05%, about0.1%, about 0.5%, about 1%, about 5%, about 10%, about 15%, about 20%,about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%,about 90%, about 95%, about 98%, about 99%, about 100%, or rangesincluding and between any two of these values and above any one of thesevalues. The reduction in the amount of adulterants may be measured bydirectly determining the adulterants in the hydroprocessed product andcomparing with the amount of adulterants in the feed stream.Alternatively, the reduction in the amount of adulterants may bemeasured by concentrating the adulterant such as through distillation,reaction, extraction, or combinations which are well known to thoseskilled in analytical chemistry. Such techniques can improve theresolution of the adulterant concentration in the respective compositiontested.

Adulterants of the present technology are typically associated with thebiorenewable feedstock employed. In some embodiments, the adulterantsinclude polymers, monomers of polymers, pesticides, additives,halogenated organic compounds, or mixtures of any two or more thereof.In some embodiments, the adulterants include dissolved adulterants,solubilized adulterants, particulate adulterants, or mixtures of any twoor more thereof. In some embodiments, the particulate adulterants areless than about 1 mm in diameter. In some embodiments, the particulateadulterants are less than about 100 μm in diameter. In some embodiments,the particulate adulterants are less than about 80 μm in diameter. Insome embodiments, the particulate adulterants are less than about 50 μmin diameter. In some embodiments, the particulate adulterants are lessthan about 10 μm in diameter. In some embodiments, the particulateadulterants are less than about 1 μm in diameter. In some embodiments,the particulate adulterants are less than about 0.1 μm in diameter.

Association of the adulterants may occur through a variety of routes andsources. For example, in meat processing plants and the rendering oftallow, animal carcasses and packaged goods may be wrapped in plasticfilms, some of which may end up in the rendered fats. Two common plasticfilms are polyethylene (PE) and polyvinylidene chloride (PVDC). Infacilities where packaged meats are recycled (e.g. when product is pastits shelf life, pieces of packaging material, plastic liners, and evenused latex gloves may become mixed in with the rendered fat. Some of thepolymeric materials and the associated additives may be incorporatedinto the fat as particulate material, solubilized material, or a mixtureof both. Similarly, in recovering waste vegetable oils and restaurantgreases, contamination by packages from the fried foods, plasticware,transfer hoses, and a multitude of other sources of contamination mayoccur. While various pretreatment steps may reduce particulate matterand even solubilized material to some degree, the solubilized polymericadulterant may still persist in the material. Some adulterants may bemonomers incorporated within the polymer or provided by decomposition ofthe polymer.

Pesticides, wood preservatives, and drugs are other adulterants that maybe associated with the biorenewable feedstock. Many drugs and pesticidesare fat soluble and may enter the food chain through consumption ofplants, grain, seeds, as well as runoff into the water system in thecase of fish (e.g. fish oil). These adulterants may end up in animal fatas well as plant oils and algal oils. Drugs are typically more common inanimal fats than in other sources of fatty acids, where the primarysource may be in the application of veterinary medicine. Woodpreservatives are expected to be less prevalent in fats and oils thanpesticides, but may enter the food supply in a similar fashion topesticides.

Food preservatives, including anti-oxidants, are other type ofadulterant that may be present in oils and fats from packaged foodoperations. Preservatives are added to packaged foods to increase theshelf life of the food.

A partial list of polymers is provided in Table 1.

TABLE 1 Examples of Polymers Abbrev. Name ABS Acrylonitrile butadienestyrene rubber ACM Polyacrylate Rubber AEM Ethylene-acrylate Rubber AUPolyester Urethane BIIR Bromo Isobutylene Isoprene BR Polybutadiene CIIRChloro Isobutylene Isoprene CR Polychloroprene CSM ChlorosulphonatedPolyethylene ECO Epichlorohydrin EP Ethylene Propylene EPDM EthylenePropylene Diene Monomer EU Polyether Urethane FEPMTetrafluoroethylene/propylene rubbers FFKM Perfluorocarbon elastomersFKM Fluoroelastomer FMQ Fluoro Silicone FPM Fluorocarbon Rubber HDPEHigh density Polyethylene HNBR Hydrogenated Nitrile Butadiene IRPolyisoprene IIR Isobutylene Isoprene rubber LDPE Low densitypolyethylene NBR Acrylonitrile Butadiene PE Polyethylene PIBPolyisobutene PP Polypropylene PS Polystyrene PVC Poly vinyl choloridePVDC Polyvinylidene chloride PU Polyurethane SBR Styrene Butadiene SEBSStyrene Ethylene Butylene Styrene Copolymer SI Polysiloxane VMQ VinylMethyl Silicone XNBR Acrylonitrile Butadiene Carboxy Monomer XSBRStyrene Butadiene Carboxy Monomer YBPO Thermoplastic Polyether-esterYSBR Styrene Butadiene Block Copolymer YXSBR Styrene Butadiene CarboxyBlock Copolymer — Latex products — Synthetic rubbers — Natural rubbers —Neoprene — Chloroprene derivatives — Fluorinated Polymers — Polyesters —Polyamides — Polyacetals

In some embodiments, the adulterants include acrylonitrile butadienestyrene thermoplastic, polyacrylate rubber, ethylene-acrylate rubber,polyester urethane, bromo isobutylene isoprene rubber, polybutadienerubber, chloro isobutylene isoprene rubber, polychloroprene,chlorosulphonated polyethylene, epichlorohydrin, ethylene propylenerubber, ethylene propylene diene monomer, polyether urethane,tetrafluoroethylene/propylene rubbers, perfluorocarbon elastomers,fluoroelastomer, fluoro silicone, fluorocarbon rubber, high densitypolyethylene, hydrogenated nitrile butadiene, polyisoprene, isobutyleneisoprene rubber, low density polyethylene, polyethylene terephthalate,ethylene vinyl acetate, acrylonitrile butadiene, polyethylene,polyisobutene, polypropylene, polystyrene, poly vinyl choloride,polyvinylidene chloride, polyurethane, styrene butadiene, styreneethylene butylene styrene copolymer, polysiloxane, vinyl methylsilicone, acrylonitrile butadiene carboxy monomer, styrene butadienecarboxy monomer, thermoplastic polyether-ester, styrene butadiene blockcopolymer, styrene butadiene carboxy block copolymer, polyesters,polyamides, polyacetals, or mixtures of any two or more thereof.

In some embodiments, the adulterants include a polymer additive. Apartial list of polymer additives is provided in Table 2.

TABLE 2 Examples of Associated Polymer Additives 1 Plastic stabilizers 2UV Stabilizers 3 Plasticizers 4 Acetamide 5 Benzyl benzoate 6 Benzylbutyl phthalate 7 Bis (2-ethylhexyl) adipate 8 Bis (2-ethylhexyl)phthalate 9 Bisphenol A 10 Bisphenol AF 11 Centralite 12 1,2-Cyclohexanedicarboxylic acid diisononyl ester 13 Dibutyl phthalate 14 Dibutylsebacate 15 D cont. 16 Diethylene glycol dinitrate 17 Diisobutylphthalate 18 Diisodecyl phthalate 19 Diisononyl phthalate 20 Dimethylmethylphosphonate 21 2,4-Dinitrotoluene 22 Dioctyl adipate 23 Dioctylterephthalate 24 Dipropylene glycol 25 Epoxidized soybean oil 26 Ethylbutyrate 27 Ethylene carbonate 28 Furoin 29 Neopentyl glycol 30Phthalate 31 Polybutene 32 Polycaprolactone 33 Propylene carbonate 34Triacetin 35 Tributyl phosphate 36 Tricresyl phosphate 37 Triethylphosphate 38 Triethylene glycol dinitrate 39 Trimethylolethanetrinitrate 40 Flame retardants 41 Asbestine 42 Barium borate 43Brominated flame retardant 44 Bromoform 45 Calcium borate 46 Chlorendicacid 47 Chlorinated paraffins 48 Cubicle curtain 49 Decabromodiphenylether 50 Defender M 51 1,2-Dibromoethane 52 Dimethyl chlorendate 53Dimethyl methylphosphonate 54 Fire-safe polymers 55 Heptazine 56Hexabromocyclododecane 57 Metepa 58 Noflan 59 Octabromodiphenyl ether 60Pentabromodiphenyl ether 61 Phos-Chek 62 Polybrominated biphenyl 63Polybrominated diphenyl ethers 64 Polychlorinated biphenyl 65Tetrabromobisphenol A 66 Tris (2,3-dibromopropyl) phosphate 67 Tris(2-chloroethyl) phosphate 68 Zinc borate 69 Halogenated Organics

In some embodiments, the adulterants include acetamide, benzyl benzoate,benzyl butyl phthalate, bis(2-ethylhexyl) adipate, bis(2-ethylhexyl)phthalate, bisphenol A, bisphenol AF, 1,2-cyclohexane dicarboxylic aciddiisononyl ester, dibutyl phthalate, dibutyl sebacate, diethylene glycoldinitrate, diisobutyl phthalate, diisodecyl phthalate, diisononylphthalate, dimethyl methylphosphonate, 2,4-dinitrotoluene, dioctyladipate, diisodecyl adipate, dipropylene glycol, epoxidized soybean oil,ethyl butyrate, ethylene carbonate, furoin, neopentyl glycol, phthalate,polybutene, polycaprolactone, propylene carbonate, triacetin, tributylphosphate, tricresyl phosphate, triethyl phosphate, triethylene glycoldinitrate, trimethylolethane trinitrate, asbestine, barium borate,brominated flame retardant, bromoform, calcium borate, chlorendic acid,decabromodiphenyl ether, 1,2-dibromoethane, dimethyl chlorendate,dimethyl methylphosphonate, heptazine, hexabromocyclododecane,octabromodiphenyl ether, pentabromodiphenyl ether, polybrominatedbiphenyl, polybrominated diphenyl ethers, polychlorinated biphenyl,tetrabromobisphenol A, tris(2,3-dibromopropyl)phosphate,tris(2-chloroethyl)phosphate, zinc borate, or mixtures of any two ormore thereof. In some embodiments, the adulterants include both apolymer and a polymer additive.

In some embodiments, the adulterants comprise hindered phenol,hydroquinone, phosphite, or thioester anti-oxidants. In someembodiments, the adulterants include styrenated phenol, alkylatedhindered phenols, 2-tert-butyl-4-methylphenol, 2- and3-tert-butyl-4-hydroxyanisole, 2,6-di-tert-butyl-p-cresol,2,6-distyrenated p-cresol, 2,6-di-tert-butyl-4-nonylphenol,2,4-bis-(n-octylthio)-6-(4-hydroxy-3′,5′-di-tert-butylanilino)-1,3,5-triazine,2,5-di-tert-amylhydroquinone, mono-tert-butylhydroquinone, hydroquinonemonomethyl ether, 2,5-di-t-butyl hydroquinone,tris(p-nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite,distearyl pentaerythritol diphosphite, dilauryl-3,3′-thio-dipropionate,distearyl-3,3′-thio-diproprionate, ditridecyl-thio-dipropionate,thiodipropionic acid, or mixtures of any two or more thereof.

In some embodiments, the adulterants include pesticides, such asinsecticides, fumigants, fungicides, herbicides, and plant growthregulators. In some embodiments, the adulterants include1-bromo-3-chloro-5,5-dimethylhydantoin, ethyl(R)-2-[4-(6-chloro-1,3-benzoxazol-2-yloxy)phenoxy]propionate,2-methyl-4-chlorophenoxyacetic acid, methyl2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)methylamino]carbonyl]amino]sulfonyl]benzoate,abamectin, acephate, acetamiprid, acetochlor(2-Chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)acetamide),aldicarb (2-methyl-2-(methylthio)propanal O—(N-methylcarbamoyl)oxime),amitraz, 3-amino-1,2,4-triazole, ancymidol, anilazine, atrazine,azinphos-methyl, azinphos-ethyl, azoxystrobin, bentazon, bifenthrin,bendiocarb, bensulide, boscalid, brodifacoum, bromadiolone, bromethalin,bromoxynil,(3aR,7aS)-2-[(trichloromethyl)sulfanyl]-3a,4,7,7a-tetrahydro-1H-isoindole-1,3(2H)-dione,carbaryl, carbathiin, carbofuran, chloroneb, chlorophacinone,chloropicrin, chlorothalonil, chlorphropham, chlorphyrifos, chlormequatchloride, clethodim, clodinafop-propargyl, clofentezine, clopyralid,clothianidin, cyfluthrin ([(R)-cyano-[4-fluoro-3-(phenoxy)phenyl]methyl](1R,3R)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylate),cyhalothrin, cymoxanil, cypermethrin, cyprodinil, cyromazine,daminozide, dazomet, (Z,E)-tetradeca-9,12-dienyl acetate, deltamethrin,desmedipham, diazinon (O,O-diethylO-[4-methyl-6-(propan-2-yl)pyrimidin-2-yl]phosphorothioate), dicamba,dichlobenil, diclofop-methyl, dicloran, 2,4-dichlorophenoxyacetic acid(“2,4-D”), dichloropropene, dichlorvos, dicofol, didecyl dimethylammonium chloride, difenoconazole, difenzoquat, dimethenamid,dimethoate, dimethomorph, dinocap, diphacinone, diquat, diuron(3-(3,4-dichlorophenyl)-1,1-dimethylurea), dodemorph acetate, dodine,endosulfan, S-ethyl N,N-dipropylcarbamothioate, ethalfluralin,ethametsulfuron-methyl, ethephon, etridiazole, fenbuconazole,fenbutatin-oxide, fenhexamid, fenoxaprop-p-ethyl, fenoxycarb, ferbam,florasulam, fluazifop-p-butyl, fludioxonil, fluoroxypyr, flusilazole,folpet, glufosinate, glyphosate, hexazinone, imazamethabenz, imazamox,imazethapyr, imidacloprid, iprodione, isoxaben, kinoprene,kresoxim-methyl, linuron, malathion, mancozeb, maneb (manganeseethylene-1,2-bisdithiocarbamate, polymer),2-methyl-4-chlorophenoxyacetic acid (MCPA),4-(4-chloro-2-methylphenoxy)butanoic acid (MCPB), mecoprop, mefenoxam,metalaxyl, metham sodium, metham potassium, methamidophos, methomyl,methoxyfenozide, methoprene, methyl bromide, metiram, metolachlor((S)-2-chloro-N-(2-ethyl-6-methyl-phenyl)-N-(1-methoxypropan-2-yl)acetamide),metribuzin, metsulfuron methyl, myclobutanil, naled(1,2-dibromo-2,2-dichloroethyl dimethyl phosphate), napropamide,naptalam, nicosulfuron, nonanoic acid, oxadiazon, oxamyl, oxycarboxin,oxyfluorfen, paclobutrazol, paraquat (1,1′-dimethyl-4,4′-bipyridiniumdichloride), pendimethalin, permethrin, phenmediphan, phosalone,phosmet, pirimicarb, prohexadione calcium, prometryne, propanil,propiconazole, propyzamide, pyraclostrobin, pyrethrin I, pyrethrin II,pyridaben, quinclorac, quintozene, rimsulfuron, sethoxydim, simazine(6-chloro-N,N′-diethyl-1,3,5-triazine-2,4-diamine), spinosyn A, spinosynD, tebuconazole, tebufenozide, tefluthrin, terbacil, terbufos,tetrachlorvinphos, thiabendazole, thiamethoxam, thifensulfuron methyl,thiophanate methyl, thiram (dimethylcarbamothioylsulfanylN,N-dimethylcarbamodithioate), tralkoxydim, triadimenol, triallate,tribenuron methyl, trichlorfon, trifluralin, triforine, trinexapac,trinexapac-ethyl, triticonazole, uniconazole, vinclozolin, warfarin, ormixtures of any two or more thereof. In some embodiments, theadulterants include carbamates, organophospates, and phenoxy components.In some embodiments, the adulterants include acephate, acetochlor(2-chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)acetamide),aldicarb (2-methyl-2-(methylthio)propanal O—(N-methylcarbamoyl)oxime),atrazine, bifenthrin, chloropicrin, chlorothalonil, chlorphyrifos,2,4-dichlorophenoxyacetic acid (“2,4-D”), dichloropropene, dimethenamid,diuron (3-(3,4-dichlorophenyl)-1,1-dimethylurea), ethephon, fenoxycarb,glyphosate, 2-methyl-4-chlorophenoxyacetic acid (MCPA), metham sodium,metham potassium, methyl bromide, metolachlor((S)-2-chloro-N-(2-ethyl-6-methyl-phenyl)-N-(1-methoxypropan-2-yl)acetamide),paraquat (1,1′-dimethyl-4,4′-bipyridinium dichloride), pendimethalin,propanil, simazine, trifluralin, or mixtures of any two or more thereof.

Any of the previously described adulterants may also be included in thefeed stream as mixtures of any two or more thereof of the adulterants.Combinations of any two or more members of the above recited groupingsof adulterants as well as combinations of any two or more of the aboverecited adulterants are within the scope of the present technology andpresently described method. In some embodiments, the adulterants includepolyvinylidene chloride and a polymer additive. In some embodiments, theadulterants include polyvinylidene chloride and a pesticide.

The fixed bed reactor is at a temperature less than about 750° F. (400°C.). In some embodiments, the temperature is from about 70° F. (20° C.)to about 750° F. (400° C.). In some embodiments, the temperature is fromabout 140° F. (60° C.) to about 750° F. (400° C.). In some embodiments,the fixed bed reactor is at a temperature falling in the range fromabout 480° F. (250° C.) to about 750° F. (400° C.). The fixed bedreactor may operate at a temperature of about 80° F. (25° C.), about100° F. (38° C.), about 150° F. (65° C.), about 200° F. (95° C.), about250° F. (120° C.), about 300° F. (150° C.), about 350° F. (175° C.),about 400° F. (205° C.), about 450° F. (230° C.), about 500° F. (260°C.), about 540° F. (280° C.), about 570° F. (300° C.), about 610° F.(320° C.), about 645° F. (340° C.), about 680° F. (360° C.), about 720°F. (380° C.), and ranges including and in between any two of thesevalues. The weighted average bed temperature (WABT) is commonly used infixed bed, adiabatic hydroprocessing reactors to express the “average”temperature of the reactor which accounts for the nonlinear temperatureprofile between the inlet and outlet of the reactor.

${WABT} = {\sum\limits_{i = 1}^{N}{\left( {WABT}_{i} \right)\left( {Wc}_{i} \right)}}$${WABT}_{i} = \frac{T_{i}^{in} + {2T_{i}^{out}}}{3}$

In the equation above, T_(i) ^(in) and T_(i) ^(out) refer to thetemperature at the inlet and outlet, respectively, of catalyst bed i. Asshown, the WABT of a reactor system with N different catalyst beds maybe calculated using the WABT of each bed (WABT_(i)) and the weight ofcatalyst in each bed (Wc_(i)).

The feed stream is combined with a hydrogen-rich treat gas. The ratio ofhydrogen-rich treat gas to biorenewable feedstock is in the range ofabout 2,000 to about 10,000 SCF/bbl (in units of normal liter of gas perliter of liquid (Nl/l), about 355 Nl/l to about 1780 Nl/l). The ratio ofhydrogen-rich treat gas to biorenewable feedstock may be about 2,500SCF/bbl (about 445 Nl/l), about 3,000 SCF/bbl (about 535 Nl/l), about3,500 SCF/bbl (about 625 Nl/l), about 4,000 SCF/bbl (about 710 Nl/l),about 4,500 SCF/bbl (about 800 Nl/l), about 5,000 SCF/bbl (about 890Nl/l), about 5,500 SCF/bbl (about 980 Nl/l), about 6,000 SCF/bbl (about1070 Nl/l), about 6,500 SCF/bbl (about 1160 Nl/l), about 7,000 SCF/bbl(about 1250 Nl/l), about 7,500 SCF/bbl (about 1335 Nl/l), about 8,000SCF/bbl (about 1425 Nl/l), about 8,500 SCF/bbl (about 1515 Nl/l), about9,000 SCF/bbl (about 1600 Nl/l), about 9,500 SCF/bbl (about 1690 Nl/l),and ranges including and in between any two of these values. Thehydrogen-rich treat gas contains contain from about 70 mol % to about100 mol % hydrogen. In terms of mass ratio, the ratio of the feed streamto hydrogen-rich treat gas is from about 5:1 to 25:1. The ratio of thefeed stream to hydrogen-rich treat gas may be about 6:1, about 7:1,about 8:1, about 9:1, about 10:1, about 11:1, about 12:1, about 13:1,about 14:1, about 15:1, about 16:1, about 17:1, about 18:1, about 19:1,about 20:1, about 22:1, about 23:1, about 24:1, and ranges including andin between any two of these values or greater than any one of thesevalues.

In some embodiments, the fixed bed reactor includes a hydrogenationcatalyst. The hydrogenation catalyst may include Co, Mo, Ni, Pt, Pd, Ru,W, NiMo, NiW, CoMo, or combinations of any two or more thereof. In someembodiments, the hydrogenation catalyst includes NiMo, NiW, CoMo, andcombinations of any two or more thereof. Supports for the hydrogenationcatalyst include alumina and alumina with silicon oxides and/orphosphorus oxides. It should be noted that one of ordinary skill in theart can select an appropriate hydrogenation catalyst to provide aparticular result and still be in accordance with the presenttechnology.

In some embodiments, the fixed bed reactor includes a hydrotreatmentcatalyst. The hydrotreatment catalyst may include Co, Mo, Ni, Pt, Pd,Ru, W, NiMo, NiW, CoMo, or combinations of any two or more thereof. Insome embodiments, the hydrotreatment catalyst includes NiMo, NiW, CoMo,and combinations of any two or more thereof. Supports for thehydrotreatment catalyst include alumina and alumina with silicon oxidesand/or phosphorus oxides. It should be noted that one of ordinary skillin the art can select an appropriate hydrotreatment catalyst to providea particular result and still be in accordance with the presenttechnology.

In some embodiments, the fixed bed reactor includes a hydroisomerizationcatalyst. The hydroisomerization catalyst may be a bifunctionalcatalyst. Bifunctional catalysts are those having ahydrogenation-dehydrogenation activity from a Group VIB and/or GroupVIII metal, and acidic activity from an amorphous or crystalline supportsuch as amorphous silica-alumina (ASA), silicon-aluminum-phosphate(SAPO) molecular sieve, mesoporous material (MCM), zirconia and/oranion-modified zirconia, or aluminum silicate zeolite (ZSM). In someembodiments the metal includes platinum, palladium, or tungsten. In someembodiments, the support includes HF-treated alumina, silica alumina,zirconia, zirconium sulfate, SAPO-11, SAPO-31, SAPO-41, MCM-41, ZeoliteY, mordenite, ZSM-22, and ZSM-48. In some embodiments, thehydroisomerization catalyst includes Pt/Pd-on-ASA or Pt-on-SAPO-11.However, it should be noted that one of ordinary skill in the art canselect an appropriate hydroisomerization catalyst to provide aparticular result and still be in accordance with the presenttechnology.

To maintain the active metal sulfide functionality of the hydrotreatmentand/or hydroisomerization catalyst despite the negligible presence oforganic sulfur in most biorenewable feedstocks, the feed stream may besupplemented with a sulfur compound that decomposes to hydrogen sulfidewhen heated and/or contacted with a catalyst. In some embodiments, thesulfur compound includes methyl mercaptan, ethyl mercaptan, n-butylmercaptan, dimethyl sulfide (DMS), dimethyl disulfide (DMDS),dimethylsulfoxide (DMSO), diethyl sulfide, di-tert-butyl polysulfide(TBPS), di-octyl polysulfide, di-tert-nonyl polysulfude (TNPS), carbondisulfide, thiophene, or mixtures of any two or more thereof. Theconcentration of the sulfur compound in the feed stream may be fromabout 50 ppm to about 2,000 ppm by weight sulfur. The feed stream mayinclude a fossil-fuel fraction wherein the fossil-fuel fraction providesthe sulfur, either in combination with or in the absence of the abovementioned sulfur compounds.

The fixed bed reactor is at a pressure falling in the range from about200 psig (about 13.8 barg) to about 4,000 psig (about 275 barg). Thepressure may be about 300 psig (21 barg), about 400 psig (28 barg),about 500 psig (34 barg), about 600 psig (41 barg), about 700 psig (48barg), about 800 psig (55 barg), about 900 psig (62 barg), about 1,000psig (69 barg), about 1,100 psig (76 barg), about 1,200 psig (83 barg),about 1,300 psig (90 barg), about 1,400 psig (97 barg), about 1,500 psig(103 barg), about 1,600 psig (110 barg), about 1,700 psig (117 barg),about 1,800 psig (124 barg), about 1,900 psig (131 barg), about 2,000psig (138 barg), about 2,200 psig (152 barg), about 2,400 psig (165barg), about 2,600 psig (179 barg), about 2,800 psig (193 barg), about3,000 psig (207 barg), about 3,200 psig (221 barg), about 3,400 psig(234 barg), about 3,600 psig (248 barg), about 3,800 psig (262 barg),about 3,900 psig (269 barg), and any ranges including and in between anytwo of these values. In some embodiments, the pressure is from about1,000 psig (69 barg) to about 2,000 psig (138 barg).

In some embodiments, the feed stream further comprises a diluent. Thediluent may include a recycled hydroprocessed product, a distilledfraction of the hydroprocessed product, a petroleum hydrocarbon fluid, asynthetic hydrocarbon product stream from a Fischer-Tropsch process, ahydrocarbon product stream produced by fermentation of sugars (e.g.farnesene), natural hydrocarbons such as limonene and terpene, naturalgas liquids, or mixtures of any two or more thereof. In someembodiments, the hydrocarbonaceous diluent includes a recycledhydroprocessed product, a distilled fraction of the hydroprocessedproduct, a petroleum hydrocarbon fluid, or mixtures of two or morethereof. The ratio of hydrocarbonaceous diluent to biorenewablefeedstock falls within the range from about 0.5:1 to about 20:1. Theratio of hydrocarbonaceous diluent to biorenewable feedstock may beabout 1:1, about 2:1, about 3:1, about 4:1, about 5:1, about 6:1, about7:1, about 8:1, about 9:1, about 10:1, about 11:1, about 12:1, about13:1, about 14:1, about 15:1, about 16:1, about 17:1, about 18:1, about19:1, and ranges including and between any two of these values.

In some embodiments, the hydroprocessed product includes a hydrogenatedproduct. In some embodiments, the hydrogenated product includes ahydrogenated free fatty acid, a hydrogenated fatty acid ester, ormixtures thereof. In some embodiments, the hydrogenated fatty acid esterincludes a hydrogenated triglyceride. In some embodiments, thehydrogenated product includes a partially hydrogenated product. In someembodiments, the hydrogenated product includes a fully hydrogenatedproduct. For example, in some embodiments, the hydrogenated productincludes a partially hydrogenated free fatty acid, a partiallyhydrogenated fatty acid ester, or mixtures thereof. In some embodiments,the hydrogenated product includes a partially hydrogenated triglyceride.In some embodiments, the hydrogenated product includes a fullyhydrogenated free fatty acid, a fully hydrogenated fatty acid ester, ormixtures thereof. In some embodiments, the hydrogenated product includesa fully hydrogenated triglyceride.

In some embodiments, the hydroprocessed product includes at least 80 wt% paraffins falling within the range of C₁₁ to C₂₄, where the paraffinsinclude C₁₆ and C₁₈ paraffins; from about 0.1 wt % to about 7.0 wt %cylcoparaffins; and from about 0.001 wt % to about 1.0 wt % aromatics.In some embodiments of such a hydroprocessed product, the hydroprocessedproduct is suitable as a diesel fuel, a diesel fuel additive, a dieselfuel blendstock, a turbine fuel, a turbine fuel additive, a turbine fuelblendstock, an aviation fuel, an aviation fuel additive, or an aviationfuel blendstock. In some embodiments of such a hydroprocessed product,the hydroprocessed product is suitable as a diesel fuel.

In some embodiments, the hydroprocessed product may contain paraffins inthe amount of about 82 wt %, about 84 wt %, about 86 wt %, about 88 wt%, about 90 wt %, about 92 wt %, about 94 wt %, about 96 wt %, about 98wt %, about 99 wt %, and any range in between any two of these values orabove any one of these values. In some embodiments, the paraffinsinclude at least about 50% wt % C₁₆ and C₁₈ paraffins. In someembodiments, the paraffins include at least about 55% wt % C₁₆ and C₁₈paraffins. In some embodiments, the paraffins include at least about 60wt % C₁₆ and C₁₈ paraffins. In some embodiments, the paraffins includeC₁₂, C₁₆, and C₁₈ paraffins. In some embodiments, the paraffins includeC₁₄, C₁₆, and C₁₈ paraffins. In some embodiments, the paraffins includeC₁₂, C₁₄, C₁₆, and C₁₈ paraffins. In some embodiments, the paraffinsinclude iso-paraffins and n-paraffins. In some embodiments where theparaffins include iso-paraffins and n-paraffins, the ratio ofiso-paraffins to n-paraffins is at least about 4:1. The ratio ofiso-paraffins to n-paraffins may be about 4.5:1, about 5:1, about 5.5:1,about 6:1, about 6.5:1, about 7:1, about 8:1, about 9:1, about 10:1,about 11:1, about 12:1, about 13:1, about 14:1, about 15:1, about 16:1,about 17:1, about 18:1, about 19:1, about 20:1, about 21:1, about 22:1,about 23:1, about 24:1, about 25:1, about 26:1, about 27:1, about 28:1,about 29:1, about 30:1, and ranges including and between any two ofthese values or above any one of these values. In some embodiments, theratio of iso-paraffins to n-paraffins is greater than about 5:1. In someembodiments, the ratio of iso-paraffins to n-paraffins is between about5:1 and about 10:1.

In some embodiments, at least 70 wt % of the iso-paraffins aremono-methyl branched paraffins. The mono-methyl branched paraffins maybe about 72 wt %, about 74 wt %, about 76 wt %, about 78 wt %, about 80wt %, about 82 wt %, about 84 wt %, about 86 wt %, about 88 wt %, about90 wt %, about 92 wt %, about 94 wt %, about 96 wt %, about 98 wt %,about 99 wt %, and ranges including and between any two of these valuesor above any one of these values. Examples of the mono-methyl branchedparaffins include, but are not limited to, 4-methyl heptadecane,3-methyl hexadecane, and 2-methyl pentadecane. The conversion of then-paraffins to iso-paraffins may produce different amounts ofmono-methyl terminal branched products (i.e. 2-methyl branched). Thus,in some embodiments of the mono-methyl branched iso-paraffins, less thanabout 30 wt % are terminal branched. In some embodiments, less thanabout 20 wt % of the mono-methyl branched iso-paraffins are terminalbranched. In some embodiments, less than about 15 wt % of themono-methyl branched iso-paraffins are terminal branched. In someembodiments, less than about 10 wt % of the mono-methyl branchediso-paraffins are terminal branched. In some embodiments, less thanabout 5 wt % of the mono-methyl branched iso-paraffins are terminalbranched. However, in some embodiments, greater than about 30 wt % ofthe mono-methyl branched paraffins are terminal branched.

In some embodiments, the hydroprocessed product contains about 0.1 wt %to about 7.0 wt % cycloparaffins. The hydroprocessed product may havecycloparaffins in the amount of about 6 wt %, about 5 wt %, about 4 wt%, about 3 wt %, about 2 wt %, about 1 wt %, about 0.9 wt %, about 0.8wt %, about 0.7 wt %, about 0.6 wt %, about 0.5 wt %, about 0.4 wt %,about 0.3 wt %, about 0.2 wt %, about 0.1 wt %, and any range includingand in between any two of these values or below any one of these values.

In some embodiments, the hydroprocessed product contains from about 1.0wt % to about 0.001 wt % aromatics. The hydroprocessed product maycontain aromatics in the amount of about 0.9 wt %, about 0.8 wt %, about0.7 wt %, about 0.6 wt %, about 0.5 wt %, about 0.4 wt %, about 0.3 wt%, about 0.2 wt %, about 0.1 wt %, about 0.09 wt %, about 0.08 wt %,about 0.07 wt %, about 0.06 wt %, about 0.05 wt %, about 0.04 wt %,about 0.03 wt %, about 0.02 wt %, about 0.01 wt %, about 0.009 wt %,about 0.008 wt %, about 0.007 wt %, about 0.006 wt %, about 0.005 wt %,about 0.004 wt %, about 0.003 wt %, about 0.002 wt %, about 0.001 wt %,and ranges including and between any two of these values or below anyone of these values. In some embodiments, the hydroprocessed productcontains less than about 0.5 wt % total aromatics. In some embodiments,the hydroprocessed product has less than about 0.01 wt % benzene. Thehydroprocessed product may contain benzene in the amount of about 0.008wt %, about 0.006 wt %, about 0.004 wt %, about 0.002 wt %, about 0.001wt %, about 0.0008 wt %, about 0.0006 wt %, about 0.0004 wt %, about0.0002 wt %, about 0.0001 wt %, about 0.00008 wt %, about 0.00006 wt %,about 0.00004 wt %, about 0.00002 wt %, about 0.00001 wt % and rangesincluding and between any two of these values or less than any one ofthese values. Such low values of benzene may be determined throughappropriate analytical techniques, including but not limited to twodimensional gas chromatography of the composition. In some embodiments,the hydroprocessed product has less than about 0.00001 wt % of benzene.

In some embodiments, the hydroprocessed product has a sulfur contentless than about 5 wppm. The hydroprocessed product may have a sulfurcontent of about 4 wppm, about 3 wppm, about 2 wppm, about 1 wppm, about0.9 wppm, about 0.8 wppm, about 0.7 wppm, about 0.6 wppm, about 0.5wppm, about 0.4 wppm, about 0.3 wppm, about 0.2 wppm, about 0.1 wppm,and ranges including and between any two of these values or less thanany one of these values. In some embodiments, the hydroprocessed producthas a sulfur content less than about 2 wppm.

In some embodiments, the hydroprocessed product has less than about 0.1wt % oxygenates. The hydroprocessed product may have oxygenates in theamount of about 0.09 wt %, about 0.08 wt %, about 0.07 wt %, about 0.05wt %, about 0.04 wt %, about 0.03 wt %, about 0.02 wt %, about 0.01 wt%, and ranges including and between any two of these values or below anyone of these values. Such low values of oxygenates can be detectedthrough appropriate analytical techniques, including but not limited toInstrumental Neutron Activation Analysis.

In some embodiments, the biorenewable feedstock may be pretreated. Suchpretreatments include, but are not limited to, degumming,neutralization, bleaching, deodorizing, or a combination of any two ormore thereof. One type of degumming is acid degumming, which involvescontacting the fat/oil with concentrated aqueous acids. Exemplary acidsare phosphoric, citric, and maleic acids. This pretreatment step removesmetals such as calcium and magnesium in addition to phosphorus.Neutralization is typically performed by adding a caustic (referring toany base, such as aqueous NaOH) to the acid-degummed fat/oil. Theprocess equipment used for acid degumming and/or neutralization mayinclude high shear mixers and disk stack centrifuges. Bleachingtypically involves contacting the degummed fat/oil with adsorbent clayand filtering the spent clay through a pressure leaf filter. Use ofsynthetic silica instead of clay is reported to provide improvedadsorption. The bleaching step removes chlorophyll and much of theresidual metals and phosphorus. Any soaps that may have been formedduring the caustic neutralization step (i.e. by reaction with free fattyacids) are also removed during the bleaching step. The aforementionedtreatment processes are known in the art and described in the patentliterature, including but not limited to U.S. Pat. Nos. 4,049,686,4,698,185, 4,734,226, and 5,239,096.

Bleaching as used herein is a filtration process common to theprocessing of glyceride oils. Many types of processing configurationsand filtration media such as diatomaceous earth, perlite, silicahydrogels, cellulosic media, clays, bleaching earths, carbons, bauxite,silica aluminates, natural fibers and flakes, synthetic fibers andmixtures thereof are known to those skilled in the art. Bleaching canalso be referred to by other names such as clay treating which is acommon industrial process for petroleum, synthetic and biological feedsand products.

Additional types of filtration may be performed to remove suspendedsolids from the biorenewable feedstock before and/or after and/or inlieu of degumming and/or bleaching. In some embodiments, rotoscreenfiltration is used to remove solids larger than about 1 mm from thebiorenewable feedstock. Rotoscreen filtration is a mechanicallyvibrating wire mesh screen with openings of about 1 mm or larger thatcontinuously removes bulk solids. Other wire mesh filters of about 1 mmor larger housed in different types of filter may be also be employed,including self-cleaning and backwash filters, so long as they providefor bulk separation of solids larger than 1 mm, such as from about 1 mmto about 20 mm. In embodiments where bleaching through clay-coatedpressure leaf filter is not used, cartridge or bag filters with micronratings from about 0.1 to about 100 may be employed to ensure that onlythe solubilized and or finely suspended (e.g. colloidal phase)adulterants are present in the feed stream. Filtration is typicallyperformed at temperatures high enough to ensure the feed stream is aliquid of about 0.1 to 100 cP viscosity. This generally translates intoa temperature range of 20° C. to 90° C. (about 70° F. to about 195° F.For example, FIGS. 1A and 1B illustrate the removal of suspended solidadulterants by wire mesh screen and bag filters.

In some embodiments, from about 100 to about 15,000 reactor volumes ofbiorenewable feedstock are processed prior to shutdown of the fixed bedhydroprocessing reactor. The reactor volumes of biorenewable feedstockprocessed may be about 200, about 300, about 400, about 500, about 600,about 700, about 800, about 900, about 1,000, about 1,100, about 1,500,about 2,000, about 2,500, about 3,000, about 3,500, about 4,000, about4,500, about 5,000, about 5,500, about 6,000, about 6,500, about 7,000,about 7,500, about 8,000, about 8,500, about 9,000, about 9,500, about10,000, about 10,500, about 11,000, about 11,500, about 12,000, about12,500, about 13,000, about 13,500, about 14,000, about 14,500, or anyrange including and between any two of these values or greater than anyone of these values.

In some embodiments, the liquid hourly space velocity (LHSV) of thebiorenewable feedstock through the fixed bed hydroprocessing reactor isfrom about 0.2 h⁻¹ to about 10.0 h⁻¹. The LHSV may be about 0.3 h⁻¹,about 0.4 h⁻¹, about 0.5 h⁻¹, about 0.6 h⁻¹, about 0.7 h⁻¹, about 0.8h⁻¹, about 0.9 h⁻¹, about 1.0 h⁻¹, about 1.2 h⁻¹, about 1.4 h⁻¹, about1.6 h⁻¹, about 1.8 h⁻¹, about 2.0 h⁻¹, about 2.2 h⁻¹, about 2.4 h⁻¹,about 2.6 h⁻¹, about 2.8 h⁻¹, about 3.0 h⁻¹, about 3.2 h⁻¹, about 3.4h⁻¹, about 3.6 h⁻¹, about 3.8 h⁻¹, about 4.0 h⁻¹, about 4.2 h⁻¹, about4.4 h⁻¹, about 4.6 h⁻¹, about 4.8 h⁻¹, about 5.0 h⁻¹, about 5.2 h⁻¹,about 5.4 h⁻¹, about 5.6 h⁻¹, about 5.8 h⁻¹, about 6.0 h⁻¹, about 6.2h⁻¹, about 6.4 h⁻¹, about 6.6 h⁻¹, about 6.8 h⁻¹, about 7.0 h⁻¹, about7.2 h⁻¹, about 7.4 h⁻¹, about 7.6 h⁻¹, about 7.8 h⁻¹, about 8.0 h⁻¹,about 8.2 h⁻¹, about 8.4 h⁻¹, about 8.6 h⁻¹, about 8.8 h⁻¹, about 9.0h⁻¹, about 9.2 h⁻¹, about 9.4 h⁻¹, about 9.6 h⁻¹, about 9.8 h⁻¹, andranges including and between any two of these values or above any one ofthese values.

In some embodiments, the biorenewable feedstock includes free fattyacids, fatty acid esters (including mono-, di-, and trigylcerides), orcombinations thereof. In some embodiments, the biorenewable feedstockincludes animal fats, animal oils, plant fats, plant oils, vegetablefats, vegetable oils, greases, or mixtures of any two or more thereof.In some embodiments, the fatty acid esters include fatty acid methylester, a fatty acid ethyl ester, a fatty acid propyl ester, a fatty acidbutyl ester, or mixtures of any two or more thereof. In someembodiments, the biorenewable feedstock comprises the fatty aciddistillate from vegetable oil deodorization. Depending on level ofpretreatment, fats, oils, and greases, may contain between about 1 wppmand about 1,000 wppm phosphorus, and between about 1 wppm and about 500wppm total metals (mainly sodium, potassium, magnesium, calcium, iron,and copper). Plant and/or vegetable oils include, but are not limitedto, soybean oil, canola oil, rapeseed oil, tall oil, tall oil fattyacid, palm oil, palm oil fatty acid distillate, palm kernel oil,jatropha oil, sunflower oil, castor oil, camelina oil, algae oil,seaweed oil, oils from halophiles, and mixtures of any two or morethereof. These may be classified as crude, degummed, and RBD (refined,bleached, and deodorized) grade, depending on level of pretreatment andresidual phosphorus and metals content. However, any of these grades maybe used in the present technology. Animal fats and/or oils as used aboveincludes, but is not limited to, inedible tallow, edible tallow,technical tallow, floatation tallow, lard, poultry fat, poultry oils,fish fat, fish oils, and mixtures of any two or more thereof. Greasesmay include, but are not limited to, yellow grease, brown grease, wastevegetable oils, restaurant greases, trap grease from municipalities suchas water treatment facilities, and spent oils from industrial packagedfood operations, and mixtures of any two or more thereof.

In some embodiments, the biorenewable feedstock comprises animal fats,poultry oil, soybean oil, canola oil, rapeseed oils, palm oil, palmkernel oil, jatropha oil, castor oil, camelina oil, algae oil, seaweedoil, halophile oils, rendered fats, restaurant greases, brown grease,yellow grease, waste industrial frying oils, fish oils, tall oil, talloil fatty acids, or mixtures of any two or more thereof. In someembodiments, the biorenewable feedstock includes animal fats, restaurantgreases, brown grease, yellow grease, waste industrial frying oils, ormixtures of any two or more thereof.

In some embodiments, the hydroprocessed product is fractionated toprovide a middle distillate fraction. In some embodiments, the middledistillate fraction is suitable as a diesel fuel. In some embodiments,the fractionation is conducted in a distillation column equipped with areboiler or stripping steam in the bottom of the column, and a condenserat the top. The reboiler or stripping steam provide the thermal energyto vaporize the heavier fraction of the hydrocarbons while the condensercools the lighter hydrocarbon vapors to return hydrocarbon liquid backinto the top of the column. The distillation column is equipped with aplurality of plates or beds of packing material wherein the rising vaporand falling liquid come into counter-current contact. The column'stemperature profile from bottom to top is dictated by the composition ofthe hydrocarbon feed and the column pressure. In some embodiments,column pressures range from about 200 psig (about 13.8 barg) to about−14.5 psig (about −1 barg). The column is equipped with one or aplurality of feed nozzles. A portion of the condenser liquid (typically10 to 90 vol %) is drawn off as overhead distillate product while therest is allowed to refluxed back to the column. In some embodiments, thecolumn separates the product into a light and a heavy hydrocarbonfraction. In some embodiments, a broad boiling hydrocarbon feed may beseparated into three or more fractions (e.g. a C₅-C₈ naphtha overheadfraction, a C₉-C₁₄ jet fuel side draw, and a C₁₅-C₁₈₊ diesel bottomsfraction). While some embodiments employ a plurality of draw-off nozzlesto fractionate the feed into multiple cuts in the same column, otherembodiments achieve the same separation using a plurality of columns inseries, each separating the feed into an overhead fraction and a bottomfraction.

In some embodiments and in lieu of hydroisomerizing, the paraffinicproduct from the HDO reaction, or a portion thereof, can behydrocracked, dehydrogenated, oligomerized, and/or reformed to produceother products or chemical feedstocks.

The present technology, thus generally described, will be understoodmore readily by reference to the following examples, which are providedby way of illustration and are not intended to be limiting of thepresent technology.

EXAMPLES Example 1

A fixed-bed hydroprocessing reactor containing two catalyst beds wasloaded with two types of hydrotreating catalyst. The bottom bed wasfilled with a high activity NiMo catalyst and the top bed with a loweractivity Mo catalyst. Both catalysts were in the oxide form when loadedand were sulfided during reactor startup.

The feedstock processed was a mixture of commercially traded animalfats, vegetable oils (including used cooking oil), and greases (a “FOG”feed). The FOG feeds contained between 52% and 88% unsaturated fattyacids, indicating that they would undergo exothermic hydrodeoxygenation,as well as adulterants. PE is used herein as an illustrative example ofan adulterant associated with the feedstock. FIG. 2 shows a histogram ofover 125 samples of adulterated feedstocks over the course of two yearsthat were analyzed for PE. The measured values of PE in the feedstocksranged from zero to 360 ppm, but individual shipments were known togreatly exceed these values.

The reactor was pressurized with hydrogen and controlled at about 1,800psig pressure (124 barg). The feedstock was pumped to the reactor at arate equivalent to 0.72 to 1.1 LHSV (vol/h FOG feed per vol NiMocatalyst). The feedstock was combined with heated hydrocarbon diluent toachieve a reactor inlet temperature within the 510° F. (266° C.) to 540°F. (282° C.) range. The hydrocarbon diluent was the product of thereaction and which was combined with feed at a 2:1 ratio (voldiluent:vol feed). Hydrogen was introduced to the reactor at a rate of5,000 SCF/bbl (890 Nl/l) along with the feed and diluent. Additionalhydrogen was introduced to the reactor as quench gas between the top andbottom beds to control the outlet temperature to a value between 680° F.(360 C) to 710° F. (377° C.). The WABT of the reactor was thus betweenabout 620° F. (327° C.) and 653° F. (345° C.). The hydrodeoxygenated(HDO) product was further processed via hydroisomerization anddistillation to provide a hydrocarbon product meeting diesel fuelspecifications (“FOG diesel”). A portion of the HDO product was recycledand used as diluent for the feed as described herein.

Notably, as shown in Table 3, the hydroprocessing of feedstocksconsistently yielded high quality FOG diesel despite the variableadulterant concentration of the feed.

TABLE 3 Comparison of PE Content of the FOG Feed and Finished FOG DieselCarbon Residue Description Year 1 Year 2 Average feedstock PE (ppm) overyear 54 20 Average diesel 10% carbon residue (wt %) 0.036 0.036 Averagecarbon residue, whole diesel 36 36 (ppm)Based upon the feedstocks processed during Year 1 and Year 2, theestimated annual average PE in the feedstock was 54 ppm and 20 ppm,respectively. During the same period of time (e.g. over 100 samplestested), the annual averages of finished diesel carbon residue (per ASTMD524) were 0.036 wt %. Converting to a whole diesel basis, this isequivalent to 36 ppm for both Year 1 and Year 2 and indicates therobustness of the present technology in successful long-term processingof adulterated feedstocks into a finished fuel. In addition, there wereno engine performance related problems associated with the renewablefuel, both in blended and neat forms, ranging from the use of the fuelin conventional on and off-road diesel applications to high performancerace engines and large locomotive engines.

Example 2

A portion of the renewable diesel product of Example 1 was distilled toproduce a biorenewable jet fuel fraction (“FOG kerosene”). Thedistillation was performed to achieve a 270° C. cut-point (target finalboiling point) for the jet fuel, consistent with final boiling pointspecification of 300° C. max.

Table 4 provides a summary of the specification test results for thebiorenewable jet fuel according to the present technology in comparisonto the industry minimum standard for synthetic jet fuel (D7566), asynthetic jet fuel produce by the Fischer-Tropsch Gas-to-Liquid (GTL)process, and a petroleum jet fuel (JP-8). The GTL jet fuel fraction(“GTL synthetic kerosene” in Table 4) was produced from conversion ofnatural gas to syngas, followed by Fischer-Tropsch synthesis. The GTLsynthetic kerosene provides a baseline for an “adulterant free” fuel. Asobserved in Table 4, the thermal stability and existent gum values(indicators of residual adulterants) for the biorenewable jet fuelproduced by the present method was the same as the “adulterant free” GTLsynthetic kerosene. Specifically, the thermal stability test at 325° C.produced no tube pressure drop (0 mm Hg) or discoloration (rating 1).This is in contrast to a 2 mm Hg observed pressure drop for the JP-8fuel at the less severe test condition of 260° C.

TABLE 4 Jet Fuel Test Results for GTL Kerosene, FOG Kerosene, andPetroleum Jet Fuel D7566 Specification for Synthetic FOG HydrocarbonsGTL kerosene JP-8 in Aviation synthetic (renewable Petroleum TurbineFuel kerosene jet fuel) Jet Fuel Acidity, mg KOH/g 0.015 max 0.003 0.0010.003 Flash point, ° C. 38.0 min 38.5 45.5 51 Density @ 15 C, kg/L0.730-0.770 0.734 0.761 0.804 Freezing point, ° C. −40.0 max −50.5 −48.7−51 Net heat of combustion, MJ/kg 42.8 min 43.8 44.2 43.2 Thermalstability Control temperature, ° C. 325 min 360 360 260 Filter pressureddrop, mmHg 25 max 0 0 2 Tube rating 3 max 1 1 1 Existent gum, mg/100 mL7 max 0.3 0.3 0.4

While certain embodiments have been illustrated and described, it shouldbe understood that changes and modifications can be made therein inaccordance with ordinary skill in the art without departing from thetechnology in its broader aspects as defined in the following claims.

The embodiments, illustratively described herein may suitably bepracticed in the absence of any element or elements, limitation orlimitations, not specifically disclosed herein. Thus, for example, theterms “comprising,” “including,” “containing,” etc. shall be readexpansively and without limitation. Additionally, the terms andexpressions employed herein have been used as terms of description andnot of limitation, and there is no intention in the use of such termsand expressions of excluding any equivalents of the features shown anddescribed or portions thereof, but it is recognized that variousmodifications are possible within the scope of the claimed technology.Additionally, the phrase “consisting essentially of” will be understoodto include those elements specifically recited and those additionalelements that do not materially affect the basic and novelcharacteristics of the claimed technology. The phrase “consisting of”excludes any element not specified.

The present disclosure is not to be limited in terms of the particularembodiments described in this application. Many modifications andvariations can be made without departing from its spirit and scope, aswill be apparent to those skilled in the art. Functionally equivalentmethods and compositions within the scope of the disclosure, in additionto those enumerated herein, will be apparent to those skilled in the artfrom the foregoing descriptions. Such modifications and variations areintended to fall within the scope of the appended claims. The presentdisclosure is to be limited only by the terms of the appended claims,along with the full scope of equivalents to which such claims areentitled. It is to be understood that this disclosure is not limited toparticular methods, reagents, compounds compositions or biologicalsystems, which can of course vary. It is also to be understood that theterminology used herein is for the purpose of describing particularembodiments only, and is not intended to be limiting.

In addition, where features or aspects of the disclosure are describedin terms of Markush groups, those skilled in the art will recognize thatthe disclosure is also thereby described in terms of any individualmember or subgroup of members of the Markush group.

As will be understood by one skilled in the art, for any and allpurposes, particularly in terms of providing a written description, allranges disclosed herein also encompass any and all possible subrangesand combinations of subranges thereof. Any listed range can be easilyrecognized as sufficiently describing and enabling the same range beingbroken down into at least equal halves, thirds, quarters, fifths,tenths, etc. As a non-limiting example, each range discussed herein canbe readily broken down into a lower third, middle third and upper third,etc. As will also be understood by one skilled in the art all languagesuch as “up to,” “at least,” “greater than,” “less than,” and the like,include the number recited and refer to ranges which can be subsequentlybroken down into subranges as discussed above. Finally, as will beunderstood by one skilled in the art, a range includes each individualmember.

All publications, patent applications, issued patents, and otherdocuments referred to in this specification are herein incorporated byreference as if each individual publication, patent application, issuedpatent, or other document was specifically and individually indicated tobe incorporated by reference in its entirety. Definitions that arecontained in text incorporated by reference are excluded to the extentthat they contradict definitions in this disclosure.

Other embodiments are set forth in the following claims.

1. A method comprising contacting a feed stream comprising abiorenewable feedstock and one or more of polymers, drugs, pesticides,or food preservatives with a hydrotreatment catalyst in a fixed bedhydroprocessing reactor to produce a hydroprocessed product with lesspolymers, drugs, pesticides, or food preservatives than the feed stream;wherein the amount of the one or more of polymers, drugs, pesticides, orfood preservatives in the feed stream is about 0.1 wppm to about 1000wppm based on the biorenewable feedstock; the fixed bed hydroprocessingreactor is at a temperature less than about 680° F.; and is at apressure from about 200 psig to about 4,000 psig.
 2. The method of claim1, wherein the hydroprocessed product comprises at least 80 wt %paraffins falling within the range of C_(ii) to C₂₄, where the paraffinscomprise C₁₆ and C₁₈ paraffins; from about 0.1 wt % to about 7.0 wt %cycloparaffins; and from about 0.001 wt % to about 1.0 wt % aromatics.3. (canceled)
 4. The method of claim 1, wherein the one or more ofpolymers, drugs, pesticides, or food preservatives compriseacrylonitrile butadiene styrene thermoplastic, polyacrylate rubber,ethylene-acrylate rubber, polyester urethane, bromo isobutylene isoprenerubber, polybutadiene rubber, chloro isobutylene isoprene rubber,polychloroprene, chlorosulphonated polyethylene, epichlorohydrinpolymer, ethylene propylene rubber, ethylene propylene diene monomerpolymer, polyether urethane, tetrafluoroethylene/propylene rubbers,perfluorocarbon elastomers, fluoroelastomer, fluoro silicone,fluorocarbon rubber, high density polyethylene, hydrogenated nitrilebutadiene rubber, polyisoprene, isobutylene isoprene rubber, low densitypolyethylene, polyethylene terephthalate, acrylonitrile butadienerubber, polyethylene, polyisobutene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyurethane, styrenebutadiene, styrene ethylene butylene styrene copolymer, polysiloxane,vinyl methyl silicone, acrylonitrile butadiene carboxy monomer rubber,styrene butadiene carboxy monomer rubber, thermoplastic polyether-ester,styrene butadiene block copolymer, styrene butadiene carboxy blockcopolymer, polyesters, polyamides, or polyacetals.
 5. The method ofclaim 1, wherein the one or more of polymers, drugs, pesticides, or foodpreservatives comprise polyvinylidene chloride.
 6. The method of claim1, wherein the one or more of polymers, drugs, pesticides, or foodpreservatives further comprise a polymer additive.
 7. (canceled)
 8. Themethod of claim 1, wherein the one or more of polymers, drugs,pesticides, or food preservatives comprise styrenated phenol,2-tert-butyl-4-methylphenol, 2- and 3-tert-butyl-4-hydroxyanisole,2,6-di-tert-butyl-p-cresol, 2,6-distyrenated p-cresol,2,6-di-tert-butyl-4-nonylphenol,2,4-bis-(n-octylthio)-6-(4-hydroxy-3′,5′-di-tert-butylanilino)-1,3,5-triazine,2,5-di-tert-amylhydroquinone, mono-tert-butylhydroquinone, hydroquinonemonomethyl ether, 2,5-di-t-butyl hydroquinone,tris(p-nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite,distearyl pentaerythritol diphosphite, dilauryl-3,3′-thio-dipropionate,distearyl-3,3′-thio-diproprionate, ditridecyl-thio-dipropionate, orthiodipropionic acid.
 9. The method of claim 1, wherein the one or moreof polymers, drugs, pesticides, or food preservatives comprise acephate,acetochlor, aldicarb, atrazine, bifenthrin, chloropicrin,chlorothalonil, chlorphyrifos, 2,4-dichlorophenoxyacetic acid,dichloropropene, dimethenamid, diuron, ethephon, fenoxycarb, glyphosate,2-methyl-4-chlorophenoxyacetic acid, metham sodium, metham potassium,methyl bromide, metolachlor, paraquat, pendimethalin, propanil,simazine, or trifluralin.
 10. The method of claim 1, wherein the feedstream comprises a biorenewable feedstock, a polymer, and a polymeradditive.
 11. The method of claim 1, wherein from about 100 to about15,000 reactor volumes of biorenewable feedstock are processed prior toshutdown of the fixed bed hydroprocessing reactor.
 12. The method ofclaim 1, wherein the liquid hourly space velocity of the biorenewablefeedstock through the fixed bed hydroprocessing reactor is from about0.2 hr⁻¹ to about 10.0 hr⁻¹.
 13. (canceled)
 14. The method of claim 1,wherein the biorenewable feedstock comprises animal fats, animal oils,plant fats, plant oils, vegetable fats, vegetable oils, or greases. 15.The method of claim 1, wherein the biorenewable feedstock comprisesanimal fats, poultry oil, soybean oil, canola oil, rapeseed oils, palmoil, palm kernel oil, jatropha oil, castor oil, camelina oil, algae oil,seaweed oil, halophile oils, rendered fats, restaurant greases, browngrease, yellow grease, waste industrial frying oils, fish oils, talloil, or tall oil fatty acids.
 16. The method of claim 1, wherein thebiorenewable feedstock comprises animal fats, restaurant greases, browngrease, yellow grease, or waste industrial frying oils.
 17. The methodof claim 1, wherein the hydroprocessed product is fractionated toprovide a middle distillate fraction.
 18. The method of claim 1, whereinthe feed stream further comprises a diluent and the volume ratio ofdiluent to biorenewable feedstock falls within the range from about0.5:1 to about 20:1.
 19. The method of claim 1, wherein thehydroprocessed product is suitable as a diesel fuel, a diesel fueladditive, a diesel fuel blendstock, a turbine fuel, a turbine fueladditive, a turbine fuel blendstock, an aviation fuel, an aviation fueladditive, or an aviation fuel blendstock.
 20. The method of claim 2,wherein the hydroprocessed product is suitable as a diesel fuel.
 21. Themethod of claim 17, wherein the middle distillate fraction is suitableas a diesel fuel.
 22. The method of claim 1, wherein the feed streamcomprises a biorenewable feedstock and any two or more of polymers,drugs, pesticides, or food preservatives.
 23. The method of claim 1,wherein the amount of the one or more of polymers, drugs, pesticides, orfood preservatives in the feed stream is about 1 wppm to about 1000 wppmbased on the biorenewable feedstock.
 24. The method of claim 1, whereinthe amount of the one or more of polymers, drugs, pesticides, or foodpreservatives in the feed stream is about 10 wppm to about 1000 wppmbased on the biorenewable feedstock.
 25. The method of claim 1, whereinthe amount of the one or more of polymers, drugs, pesticides, or foodpreservatives is reduced by at least about 30%.
 26. The method of claim1, wherein at least a portion of the one or more of polymers, drugs,pesticides, or food preservatives are converted into hydroprocessedproduct.
 27. The method of claim 1, wherein the fixed bedhydroprocessing reactor is at a temperature from about 480° F. to about645° F.
 28. A method comprising contacting a feed stream comprising abiorenewable feedstock and any two or more of polymers, drugs,pesticides, or food preservatives with a hydrotreatment catalyst in afixed bed hydroprocessing reactor to produce a hydroprocessed productwith less of the any two or more of polymers, drugs, pesticides, or foodpreservatives than the feed stream; wherein the amount of the any two ormore of polymers, drugs, pesticides, or food preservatives in the feedstream is about 0.1 wppm to about 1000 wppm based on the biorenewablefeedstock; the fixed bed hydroprocessing reactor is at a temperaturefrom about 480° F. to about 680° F.; is at a pressure from about 200psig to about 4,000 psig; and the any two or more of polymers, drugs,pesticides, or food preservatives are reduced by at least about 30%. 29.(canceled)
 30. The method of claim 28, wherein the hydroprocessedproduct is suitable as a diesel fuel, a diesel fuel additive, a dieselfuel blendstock, a turbine fuel, a turbine fuel additive, a turbine fuelblendstock, an aviation fuel, an aviation fuel additive, or an aviationfuel blendstock.
 31. A method comprising contacting a feed streamcomprising a biorenewable feedstock and one or more of drugs,pesticides, or food preservatives with a hydrotreatment catalyst in afixed bed hydroprocessing reactor to produce a hydroprocessed productwith less drugs, pesticides, or food preservatives adulterants than thefeed stream; wherein the amount of one or more of drugs, pesticides, orfood preservatives in the feed stream is about 0.1 wppm to about 1000wppm based on the biorenewable feedstock; the fixed bed hydroprocessingreactor is at a temperature from about 480° F. to about 680° F.; and isat a pressure from about 200 psig to about 4,000 psig.
 32. The method ofclaim 31, wherein the amount of one or more of drugs, pesticides, orfood preservatives in the feed stream is about 10 wppm to about 1000wppm based on the biorenewable feedstock.
 33. The method of claim 31,wherein the hydroprocessed product is suitable as a diesel fuel, adiesel fuel additive, a diesel fuel blendstock, a turbine fuel, aturbine fuel additive, a turbine fuel blendstock, an aviation fuel, anaviation fuel additive, or an aviation fuel blendstock.
 34. The methodof claim 1, wherein the feed stream comprises a biorenewable feedstockand a polymer.